Polyisocyanuric acid emulsifying agents and derivatives

ABSTRACT

A mixture of molecules containing all of the following groups exhibit surface activity: isocyanurate, hydrogen-substituted isocyanurate, metal substituted isocyanurate, and at least one group selected from the class consisting of a monovalent organic radical selected from the following: isocyanate urethane (NHCO2R&#39;&#39;), urea (-NHCONHR&#39;&#39;), amino (-NH2, -NHR&#39;&#39;, or -NR2&#39;&#39;).

United States Patent Argabright et al.

POLYISOCYANURIC ACID EMULSIFYING AGENTS AND DERIVATIVES Inventors: PerryA. Argabright, Larkspur; C.

Travis Presley, Littleton, both of Colo.

Marathon Oil Company, Findlay, Ohio Filed: Feb. 9, 1972 Appl. No.:224,904

Assignee:

US. Cl 252/312, 252/356, 252/357, 260/775 NC, 260/248 NS, 260/292 TNInt. Cl C08g 22/00 Field of Search 252/312, 356, 357; 260/775 NC, 248NS, 29.2 TN

References Cited UNITED STATES PATENTS Argabright et al 260/775 Dec. 18,1973 OTHER PUBLICATIONS Noller, Chemistry of Organic Compounds, W. B.Saunders C0., Philadelphia, 195l, p. 186.

Primary Examiner-D0nald E. Czaja Assistant Examiner-M. J. WelshAttorney-Joseph C. Herring et al.

[57] ABSTRACT 7 Claims, 4 Drawing Figures POLYISOCYANURIC ACIDEMULSIFYING AGENTS AND DERIVATIVES CROSS REFERENCES TO RELATEDAPPLICATIONS The following United States Patent applications relate tothe general field of the present invention:

Ser. No. 715,199, filed Mar. 22, 1968',

Ser. No. 89,883, filed Nov. 16, 1970;

Ser. No. 72,388, filed Sept. 15, 1970;

Ser. No. 72,288, filed Sept. 15, 1970;

Ser. No. 157,236, filed June 28, 1971;

BACKGROUND OF THE INVENTION lv Field of the lnvention W The presentinvention relates to compositionssurface active generally classified inthe United States Patent Office in Class 252, subclasses -351 and -353through -358.

2. Description of the Prior Art A search in the United States PatentOffice disclosed the following prior art: US. Pat. No. 3,072,654 teachescalcium di (dichloroisocyanurate) in bleaching and cleaningcompositions; US. Pat. No. 3,272,813 complexes chloroisocyanurates withpotassium to make bleaching compositions (see column 16, lines 63-70;and US. Pat. No. 3,489,696 forms polyimides from isocyanurates andpolycarboxylic acids and mentions use of biuret triisocyanate at column5, line 62.

SUMMARY OF THE INVENTION General Statement of the Invention The presentinvention relates to a new class of compounds which are useful asemulsifying agents, e.g., in forming dispersions and emulsions. Thesecompounds are characterized by containing in a single molecule all ofthe following groups:

isocyanurate:

hydrogen-substituted isocyanurate:

and at least one group selected from the class consisting of: amonovalent organic radical selected from the following: isocyanate,urethane (-NHCO R), urea (-NHCONHR'), amino (-NH -NHR or NHR and may ormay not contain in addition to the above, metal substitutedisocyanurate:

The compounds of the present invention have the general structure shownin FIG. 1; where:

R divalent hydrocarbon or substituted hydrocarbon radical, as describedbelow and exemplified in FIG. 2

X a metal, or hydrogen or quaternary ammonium (which for the purposes ofthis invention, acts like a metal) or a combination thereof.Particularly preferred are hydrogen, quaternary ammonium and metalsselected from the following groups of the Periodic Table; Ia, Ib,1Ia,IIb, Illa, 11117, [V0, IVb, Va, Vb, Vla; including such metals as Li,Na, K, Rb, Cs, Ca, Ag, Au, Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd, Hg, B, Al,Sc, Y, La, and the other rare earths, Ac, Ga, In, T1,Ti, Zr, Hf, Ge, Sn,Pb, V, Nb, Ta, Sb, Bi, Cr, Mo, W, Mn, Fe, Ru, Co, Ni, Rh, Pd, Os, andIr.

A a monovalent organic radical selected from the following:

isocyanate urethane (-NHCO R urea (-NHCONHR'), amino (-NH -NI-IR' or -NRR monovalent hydrocarbon or substituted hydrocarbon radical, asdiscussed below;

M average number of trisubstituted isocyanurate rings and is a positiveinteger from 0 to about 400, and most preferably from 0 to about 200,

Q average number of isocyanuric acid groups and is a positive integerfrom 1 to about 10,000, more preferably from 2 to about 1000, and mostpreferably from 3 to about 100,

N-Q average number of isocyanurate salt groups and is a positive integerfrom 0 to about 10,000 more preferably from 1 to about 1,000 and mostpreferably from 2 to about 100,

2M+N+1 average number of divalent R groups and is a positive integerfrom 2 to about 1 1,000, more preferably from 3 to about 1,100 and mostpreferably from 4 to about 140,

M+2 average number of A groups and is a positive integer from 2 to about2,000, more preferably from 2 to about 400 and most preferably from 2 toabout 200;

and wherein there are no N-to-N bonds, no A-to-N bonds, no A-to-A bonds,and no R-to-R bonds.

R preferably contains two to 40, more preferably two to 30, and mostpreferably two to 18 carbon atoms.

R preferably contains one to 40 carbon atoms, more preferably one to 20carbon atoms and most preferably R and/or R can be substituted withgroups that do not interfere in the products subsequent utility or inits preparation. Examples of such non-interfering groups are: -NO C1, F,Br, 1, CN, -CO R", CO-R, --O-R", SR", NR --CONR SO R,

SO -SO-, phenyl naphthyl, alkyl (one-40 carbon atoms), PO R, cyclohexyl,cyclopropyl, polymethylene (e.g., tetramethylene), -OCOR",

etc. where R may be hydrogen, lower alkyl (e.g., ethyl, hexyl) or aryl(e.g., monovalent radicals corresponding to the aryl radicals describedin FIG. 2. The examples of R (shown in FIG. 2) are set forth forpurposes of elucidation, not restriction.

It will be recognized that the values of M, N, and Q described above areon the basis of the integers which will be used to describe a singlemolecule. In actual practice, the invention will involve mixtures ofmolect'iles'of the general form described above. Thus, the average valueofM for the mixture may be from about 1 to about 350, more preferablyfrom about 1 to 200, and most preferably from about 1 to 100; theaverage value ofQ may be from about 1.5 to 9,000, more preferably fromabout 2.0 to 1,000, and most preferably from about 3.0 to 100; the valueof N-Q may be from about to 9,000, more preferably from 0.1 to 800, andmost preferably from 0.5 to 200.

UTILITY OF THE INVENTION The present invention relates to a new class ofemulsifying agents, their preparation, and processes for their use. Forexample, the compounds of the present invention may be added toimmiscible mixtures of water and organic compounds, e.g., equal parts byvolume of water and a hydrocarbon and the resulting mixture agitated toform emulsions. This result is all the more surprising as many of thecompounds are only very slightly soluble in either phase.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows the general formula ofthe products of the present invention.

FIGS. 2 and 3 exemplify some of the possible structures of R groups ofthe starting materials and products of the present invention.

FIG. 4 shows the general formula of the organic starting materials ofthe present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Starting Materials: Thestarting materials for the present invention are metal salts ofpolyisocyanuric acids produced according to the techniques taught incopending United States Pat. No. 3,573,259 issued Mar. 30, 1971, byreacting a metal cyanate and an organic diisocyanate in the presence ofan aprotic solvent to form isocyanurate-containing polyisocyanate metalsalts.

It has been discovered that aqueous solutions of the aforementionedisocyanurate salts, of the general formula shown in FIG. 4, (where thelettered groups are as described above under Summary of the Invention),under acid conditions (i.e., pH below 6,) give the product shown inFIG. 1. The product is dramatically less soluble in water than is thepolyisocyanurate salt reactant. Suitable acids include mineral acidse.g., l-ICl, H 80 HNO and carboxylic acids, e.g., acetic acid. ReactionMedia: Water or mixtures of water and an alcohol, ketone, ester, amide,sulfoxide, sulfone, etc.

Temperature: While not narrowly critical, temperatures in the range from10 to about 200C. are preferred, with 15150C. being more preferred and20- 120C. being most preferred. The lower limit is generally thefreezing point of solution and the upper limit is generally the boilingpoint of the solution at the reaction pressure.

Pressure: While not narrowly critical, the reaction can be carried outat pressures of from 0.5 to 100, with 0.6 to 50 being more preferred,and 0.7 to 10 atmospheres being most preferred.

Time: The reaction time, of course, is dependent on the initialconcentration of the starting materials and the temperature. Thepreferred time is from 0.01 to 4500 hours, more preferred 0.05 to 350hours and most preferred from 0.06 to 200 hours.

Examples:

EXAMPLE I Preparation of Polyisocyanurate Salt To a stirred slurry of82.4 KOCN (1.02 mole) in 2000 ml of dimethylformamide (DMF) at C. 183gof tolylene diisocyanate (1.05 mole) is added at a rate of 0.85 ml/min.by means of a syringe pump.

The entire operation is carried out in a nitrogen atmosphere. Followingthe addition, the reaction mixture is stirred an additional 10 minutes,the temperature lowered to 60C., dry methanol added (large excess), andallowed to react for an additional hour to insure complete quenching.The major product is insoluble in DMF and thus readily separated by asingle filtration. A trace DMF soluble product is obtained after solventstripping the filtrate. After vacuum drying at C. to remove residual DMFand methanol, the following yield and analytical data are obtained:

Aryl/end Average Product Group M01. Yield Ratio (2M+N+l/M+Z) (Min) Wt.DMF insoluble 87,0 14.5 8,000 DMF soluble 12.0 1.5 750 1) corrected forresidual DMF (2) measured by nuclear magnetic resonance spectroscopycontains 20.9% DMF of salvation.

EXAMPLE II Preparation of Polyisocyanuric Acid The polyisocyanurateproduct (DMF insoluble) of Example I is dissolved in water to give a 7%(by weight) solution. The pH of this solution is adjusted to 5.5 byadding aqueous HCl. The conversion is substantially immediate. Theproduct is a water-insoluble solid. Aliquots of this suspension are usedfor testing without further purification.

EXAMPLES III V The utility of the polyisocyanuric acid as an emulsifyingagent is demonstrated in the following manner.

To a graduate, containing 10 ml of n-heptane (or benzene as described inTable 1), and 10 ml of water (deionized and distilled) is added 2 ml of7 weight percent aqueous solution of the polyisocyanurate salt describedin Example 1. Additional hydrochloric acid is added to provide the pI-Istated in Table 1. Subsequent shaking provides a stable emulsion havingthe volume indicated in Table l.

TABLE I Example pH Emulsion Water Hydrocarbon No. Phase Phase (m Ill 353.6 n-Hcplane IV 1.0 I) 3.8 n-Hcptanc V 1.0 21 2.4 Benzene MODIFICATIONSOF THE INVENTION It should be understood that the invention is capableof a variety of modifications and variations which will be made apparentto those skilled in the art by a reading of the specification and whichare to be included within the spirit of the claims appended hereto.

What is claimed is:

1. A composition comprising a mixture of compounds comprising in asingle molecule isocyanurate, metal isocyanurate, and having thestructure:

R divalent hydrocarbon or substituted hydrocarbon radical, containingtwo to about 40 carbon atoms,

X is selected from the group consisting of metals, hy-

drogen, or quaternary ammonium radicals,

A is a monovalent organic radical selected from the group consisting ofNI-ICO R', NI-ICONI-IR', -NH -NHR, and -NR' R is a monovalenthydrocarbon radical or substituted hydrocarbon radical containing fromone to about 40 carbon atoms,

M is the average number of trisubstituted isocyanurate rings permolecule and is a positive integer from 0 to about 400,

Q is the average number of isocyanuric acid groups and is a positiveinteger from 1 to about 10,000, 2M+N+l the average number of divalent Rgroups and is a positive integer from 2 to about 11,000, M+2 is theaverage number ofA groups and is a positive integer from 2 to about2,000, and wherein there are no N-to-N bonds, no A-to-N bonds, no

A-to-A bonds, and no R-to-R bonds,

N-Q is the average number of isocyanurate salt groups and is a positiveinteger from O to about 10,000.

2. A composition according to claim 1 wherein R is selected from thegroup of organic radicals shown below:

CaHr CHa-C H-CHa-CH;

Gib-CHr-(f H CH;

CHI-C H=CH1 (where H1=F, Cl, Br or I),

a a *i@ P OaCHa -maas COzCH:

COzCHs III 3. Compositions according to claim 1 wherein X is selectedfrom the group consisting of hydrogen, quaternary ammonium radicals andmetal radicals selected from the following groups of the Periodic Table;Ia, lb, Ila, llb, llla, lllb, lVa, lVb, Va, Vb, Vla

4. Compositions according to claim 1 wherein M is a positive integerfrom O to about 200, wherein Q is a positive integer from 3 to about100, and N-Q is from 2 to about 100, and wherein 2M+N+l is a positiveinteger from 4 to about 140, and wherein M+2 is a positive integer fromabout 2 to about 200.

5. Compositions according to claim 1 wherein R is selected from thegroup of organic radicals shown in the structure below:

CIIH; $3117 CH1"? H-CHz-CH;

CIHa CHq-CHg- C H CH: C H=CH1 I'll C H=CH2 POaCH; H1

IIsCi 35 and the substitute derivatives thereof which are substitutedwith radicals selected from the group consisting of NO, Cl, F, Br, I,CN, CO R', COR",

O-R", SR", NR CONR -SO R, SO -SO, phenyl, naphthyl, PO R", cyclo- 0hexyi, cyclopropyl, polymethylene, OCOR", and

NCOR 45 where R" may be hydrogen or lower alkyl or aryl.

6. A composition according to claim 1 wherein R contains from one to 10carbon atoms and is selected from the group consisting of CH C H C H 7.An emulsion comprising both water and at least one composition accordingto claim 1.

2. A composition according to claim 1 wherein R is selected from the group of organic radicals shown below:
 3. Compositions according to claim 1 wherein X is selected from the group consisting of hydrogen, quaternary ammonium radicals and metal radicals selected from the following groups of the Periodic Table; Ia, Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb, VIa
 4. Compositions according to claim 1 wherein M is a positive integer from 0 to about 200, wherein Q is a positive integer from 3 to about 100, and N-Q is from 2 to about 100, and wherein 2M+N+1 is a positive integer from 4 to about 140, and wherein M+2 is a positive integer from about 2 to about
 200. 5. Compositions according to claim 1 wherein R is selected from the group of organic radicals shown in the structure below:
 6. A composition according to claim 1 wherein R'' contains from one to 10 carbon atoms and is selected from the group consisting of -CH3, -C2H5, -C3H7, i-C3H7,
 7. An emulsion comprising both water and at least one composition according to claim
 1. 